Improving Orientation, Packing Density, and Molecular Arrangement in Self-Assembled Monolayers of Bianchoring Ferrocene-Triazole Derivatives by "Click" Chemistry.

This work describes the self-assembled monolayers (SAMs) of two ferrocene derivatives with two anchoring groups (at the bottom and at the top of the SAM) deposited on ultraflat template-stripped gold substrates by cyclic voltammetry and analyzed by complementary surface characterization techniques. The SAM of each molecule is deposited by three different protocols: direct deposition (one step), click reaction on the surface (two steps), and reverse click reaction on the surface (two steps). The SAM structure is well studied to determine the SAM orientation, SAM arrangement, and ferrocene position within the SAM. Electron transfer kinetics have also been studied, which agree with the quality of each SAM. With the help of two anchoring groups and click-chemistry active functional groups, we have shown that the two molecules can be deposited by controlling the position of ferrocene at either end. We further investigated the involvement of the triazole five-membered ring in the electron transfer mechanism. We have found that a carbon spacer between ferrocene and triazole improves the SAM packing. This study enhances the understanding of tethering thiol and thiol acetate anchoring groups on gold by a controlled orientation, which may help in the development of functional molecular devices requiring two anchoring groups.

Plasmonic Nanocomposites Based on Silver Nanocube-Polymer Blends Displaying Nearly Perfect Absorption in the UV Region.

Plasmonic nanocomposites based on well-dispersed silver nanocubes in poly(vinylpyrrolidone) are presented that are solution-processed into layers of varying volume fractions of nanocubes. We show that the high-energy modes of the nanocubes are almost insensitive to plasmonic coupling within the nanocube assemblies, leading to a linear increase in light absorption in the UV region with the nanocube densities. Concerning the main dipolar resonance mode at 450 nm, it is strongly affected by the formation of these assemblies, leading to an increased absorption in the UV region as well as a large absorption band in the visible region. Simulations of the optical response of the nanocube assemblies as a function of nanocube spacing and electric field polarization reveal that optical features in the visible region are due to intercube couplings at short intercube distances and parallel electric field orientation. In contrast, the additional plasmonic band in the UV region has its origin in residual dipolar oscillations of the nanocubes in combination with weak dipolar coupling for both parallel and transversal field polarizations. The combination of these effects leads to an enlarged absorption band in the UV region with nearly perfect light absorption of 98.8% at a high silver volume fraction of 8% that is accompanied by a very weak specular reflection of only 0.28%. Although such perfect absorption is usually observed only when nanocubes are assembled on a gold surface, nearly perfect absorption herein is achieved on a large palette of substrates including glass, plastic, and cheap metals such as aluminum, making it a promising approach for solution-processed robust and cheap quasi-perfect absorption coatings.

Optical response of heterogeneous polymer layers containing silver nanostructures.

This work is focused on the study of the optical properties of silver nanostructures embedded in a polymer host matrix. The introduction of silver nanostructures in polymer thin films is assumed to result in layers having adaptable optical properties. Thin film layers with inclusions of differently shaped nanoparticles, such as nanospheres and nanoprisms, and of different sizes, are optically characterized. The nanoparticles are produced by a simple chemical synthesis at room temperature in water. The plasmonic resonance peaks of the different colloidal solutions range from 390 to 1300 nm. The non-absorbing, transparent polymer matrix poly(vinylpyrrolidone) (PVP) was chosen because of its suitable optical and chemical properties. The optical studies of the layers include spectrophotometry and spectroscopic ellipsometry measurements, which provide information about the reflection, transmission, absorption of the material as well as the complex optical indices, n and k. Finite difference time domain simulations of nanoparticles in thin film layers allow the visualization of the nanoparticle interactions or the electric field enhancement on and around the nanoparticles to complete the optical characterization. A simple analysis method is proposed to obtain the complex refractive index of nanospheres and nanoprisms in a polymer matrix.

Optical modeling and optimizations of Cu2ZnSnSe4 solar cells using the modified transfer matrix method.

The fast and computationally inexpensive Modified Transfer Matrix Method (MTM) is employed to simulate the optical response of kesterite Cu2ZnSnSe4 solar cells. This method can partially take into account the scattering effects due to roughness at the interfaces between the layers of the stack. We analyzed the optical behavior of the whole cell structure by varying the thickness of the TCO layer (iZnO + ITO) between 50 and 1200 nm and the buffer CdS layer between 0 and 100 nm. We propose optimal combinations of the TCO/CdS thicknesses that can locally maximize the device photocurrent. We provide experimental data that qualitatively confirm our theoretical predictions.

Metamaterial filters at optical-infrared frequencies.

We propose two distinctive designs of metamaterials demonstrating filtering functions in the visible and near infrared region. Since the emissivity is related to the absorption of a material, these filters would then offer a high emissivity in the visible and near infrared, and a low one beyond those wavelengths. Usually, such a system find their applications in the thermo-photovoltaics field as it can find as well a particular interest in optoelectronics, especially for optical detection. Numerical analysis has been performed on common metamaterial designs: a perforated metallic plate and a metallic cross grating. Through all these structures, we have demonstrated the various physical phenomena contributing to a reduction in the reflectivity in the optical and near infrared region. By showing realistic geometric parameters, the structures were not only designed to demonstrate an optical filtering function but were also meant to be feasible on large surfaces by lithographic methods such as micro contact printing or nano-imprint lithography.

Flat-top and patterned-topped cone gratings for visible and mid-infrared antireflective properties.

Achieving a broadband antireflection property from material surfaces is one of the highest priorities for those who want to improve the efficiency of solar cells or the sensitivity of photo-detectors. To lower the reflectance of a surface, we are concerned with the study of the optical response of flat-top and patterned-topped cone shaped silicon gratings, based on previous work exploring pyramid gratings. Through rigorous numerical methods such as Finite Different Time Domain, we first designed several flat-top structures that theoretically demonstrate an antireflective character within the middle infrared region. From the opto-geometrical parameters such as period, depth and shape of the pattern determined by numerical analysis, these structures have been fabricated using controlled slope plasma etching processes. In order to extend the antireflective properties up to the visible wavelengths, patterned-topped cones have been fabricated as well. Afterwards, optical characterizations of several samples were carried out. Thus, the performances of the flat-top and patterned-topped cones have been compared in the visible and mid infrared range.

Optical properties of dielectric thin films including quantum dots.

Depending on the minimum size of their micro/nanostructure, thin films can exhibit very different behaviors and optical properties. From optical waveguides down to artificial anisotropy, through diffractive optics and photonic crystals, the application changes when decreasing the minimum feature size. Rigorous electromagnetic theory can be used to model most of the components, but, when the size is a few nanometers, quantum theory also has to be used. The materials, including quantum structures, are of particular interest for many applications, in particular for solar cells because of their luminescent and electronic properties. We show that the properties of electrons in periodic and nonperiodic multiple quantum well structures can be easily modeled with a formalism similar to that used for multilayer waveguides. The effects of different parameters, in particular the coupling between wells and well thickness dispersion, on possible discrete energy levels or the energy band of electrons and on electron wave functions are given. When such quantum confinement appears, the spectral absorption and extinction coefficient dispersion with wavelength are modified. The dispersion of the real part of the refractive index can be deduced from the Kramers-Kronig relations. Associated with homogenization theory, this approach gives a new model of the refractive index for thin films including quantum dots. The bandgap of ZnO quantum dots in solution obtained from the absorption spectrum is in good agreement with our calculation.

Bringing some photonic structures for solar cells to the fore.

A review on the use of photonic structures enabling a better absorption of solar radiation within solar cells is proposed. Specific geometric configurations, such as folded solar cells or fiber-based architectures, are shown to be promising solutions to reach better light absorption. Electromagnetic optimization of thin-film solar cells and the use of angular thin-film filters, proposed by several research groups, also provide solutions to better concentrate solar radiation within the active layers of solar cells. Finally, results on "photonized" solar cells comprising gratings or more advanced photonic components, such as photonic crystals or plasmonic structures, and their effects on light-matter interaction in solar cells are highlighted.

Sand-castle biperiodic pattern for spectral and angular broadening of antireflective properties.

This Letter deals with the antireflective properties of top-patterned pyramids, looking like sand castles, bi-periodically repeated on a silicon surface. It is demonstrated numerically that such an original pattern allows a dramatic spectral and angular broadening of the antireflective efficiency. Design examples are given for wavelengths ranging from 0.5 microm to 5 microm and incidence angles of 30 degrees and 45 degrees. Applications of such antireflective surfaces on photodetectors and solar cells are soon expected.

Optical modeling of organic solar cells based on CuPc and C60.

We have investigated the influence of the poly(3,4-ethylenedioxythiophene)-blend-poly(styrene-sulfonate) (PEDOT:PSS) layer on the short-circuit current density (J(sc)) of single planar heterojunction organic solar cells based on a copper phthalocyanine (CuPc)-buckminsterfullerene (C(60)) active layer. Complete optical and electrical modeling of the cell has been performed taking into account optical interferences and exciton diffusion. Comparison of experimental and simulated external quantum efficiency has allowed us to estimate the exciton diffusion length to be 37 nm for the CuPc and 19 nm for the C(60). The dependence of short-circuit current densities versus the thickness of the PEDOT:PSS layer is analyzed and compared with experimental data. It is found that the variation in short-circuit current densities could be explained by optical interferences.

Optical characterizations of ZnO, SnO2, and TiO2 thin films for butane detection.

The optogeometric properties of various sensitive thin films involved in gas sensing applications are investigated by using the m-line technique and atomic force microscopy. Variations of these optical properties are studied under butane and ozone exposure.

Theoretical study of amplitude and phase filtering of guided waves.

The design of integrated optics filters by use of refinement software based on the Abelès thin-film computation method and the film mode matching method is studied. The results obtained with the two computation methods are compared. Good agreement is obtained provided that the fill factor of the guided mode in the component is high and that modal losses between waveguide sections are simulated by absorption with the Abelès computation method. Integrated optics devices that manage either the amplitude of guided waves such as a dense wavelength division multiplexing narrow-bandpass filter and a gain-flattening filter or the phase of guided waves such as a broadband dispersion compensator are

Guided-wave technique for the measurement of dielectric thin-film materials' thermal properties.

A pump-and-probe setup that uses a totally reflecting prism coupler is presented. Its electromagnetic and thermal models are described. To our knowledge, the first results are given concerning the measurement of thermal properties of thin films.

Deltan/deltaT measurements performed with guided waves and their application to the temperature sensitivity of wavelength-division multiplexing filters.

Measurements of deltan/deltaT of thin films by the m-lines technique are presented. The importance of the substrate material is shown. An example of the wavelength shift of an optical thin-film filter with temperature is studied both theoretically and experimentally. The theoretical wavelength shift of a dense wavelength-division multiplexing filter is discussed.

Artificial anisotropy and polarizing filters.

The calculated spectral transmittance of a multilayer laser mirror is used to determine the effective index of the single layer equivalent to the multilayer stack. We measure the artificial anisotropy of photoresist thin films whose structure is a one-dimensional, subwavelength grating obtained from interference fringes. The limitation of the theory of the first-order effective index homogenization is discussed. We designed normal-incidence, polarizing coating and a polarization rotator by embedding anisotropic films in simple multilayer structures.